This invention relates to the use of the ketones having the structures: ##STR2## the ketoesters having structures: ##STR3## and the alcohol having the structure: ##STR4## taken alone or in combination as repellents against house flies (Musca domestica L. (Diptera: Muscidae)) and mosquitoes (Aedes aegyptae). This invention also relates to the use of the ester having the structure: ##STR5## as an attractant for house flies (Musca domestica L. (Diptera: Muscidae)) and mosquitoes (Aedes aegyptae).
This invention also relates to apparatus useful in determining the attractancy for insects of such molecules including said ester having the structure: ##STR6## and the repellency against insects of such ketones, ketoesters and alcohol having the structures: ##STR7## (i) which apparatus comprises active and passive insect interest electronic detecting, measuring and recording means collectively denoted as "DMR" means which is connected to an electric power supply source comprising detecting means, measuring means and recording means;
(ii) enclosed insect feeding and/or stimulating means collectively denoted as "IFS" means having controlled limited excess to the external environment surrounding said apparatus and associated with the said "DMR" means, and including said detecting means, said "IFS" means being located at a fixed "IFS" means location defined according to X, Y and Z coordinates having a defined first 3-space, said "IFS" means consisting essentially of: PA1 (iii) steady state direct infra-red, ultra-violet or monochromatic or polychromatic visible light radiation means for supplying at least one beam of infra-red, ultra-violet or monochromatic or polychromatic visible light radiation having a given substantially constant intensity or intensities and wave length or wave lengths to said "IFS" means location, said beam(s) of radiation being directed in a direction perpendicular to the plane of said lamina along a directional vector from below said insect attractant quantitative detecting means; and PA1 (iv) steady state air and treatment agent supply and conduction means denoted as "SAC" means for supplying and conducting air and treatment agent (e.g., one of the ketones, ketoesters, alcohol and/or ester of our invention) at a substantially constant flow rate and substantially constant linear velocity into said defined 3-space in a direction substantially parallel to the plane of said lamina at a location below said lamina simultaneously with the supplying of the beam of radiation to said "IFS" means location said insect feeding and/or stimulating lamina being constructed and said detection means being constructed so that said "DMR" means are sensitive to the completion of a circuit of electron flow through or proximate said conductive elements of said insect attractant quantitative detecting means whereby the number and frequency of the insects attracted relative to the attractancy of said radiation means to the proximity of said "IFS" means is capable of being determined using said "DMR" means. PA1 (a) an insect feeding or stimulating surface comprising at two spaced electrically conductive elements connected to said measuring and recording means, said elements having such diameters and spacing from one another as to cause an attracted insect to complete a circuit of electron flow through said conductive elements; PA1 (b) immediately beneath said insect feeding or stimulating surface a composition of matter comprising molecules to be tested for attractancy and repellency; PA1 (c) immediately beneath said molecules to be tested, a stimulant or feeding stimulant composition for said insects;
(a) a substantially horizontally-positioned insect feeding and/or stimulating microporous substantially planar lamina which is a porous membrane having an upper outer surface and a lower inner surface, said lamina being located immediately above said enclosed "IFS" means; PA2 (b) an insect attractant quantitative detecting means located immediately below said lamina and within said enclosed "IFS" means comprising at least two spaced electrically conductive elements; PA2 (c) located on said upper outer surface of said lamina a feeding stimulant composition or stimulant compositions for insects;
1. connected to said "DMR" means; and PA3 2. capable of forming a complete circuit, said elements having such dimensions and spacing from one another as to cause an attracted insect to complete a circuit of electron flow through or proximate to said elements;
Compositions of matter taken alone or for use in combination with other perfumes for repelling house flies as well as apparatus used in determining such repellency have been indicated to exist in U.S. Pat. No. 4,759,228 issued on July 26, 1988 (assigned jointly to International Flavors and Fragrances Inc. and The University of Florida). U.S. Pat. No. 4,759,228 discloses the use of 1-nonen-3-ol in repelling house flies. Furthermore, formulations exist in commerce which are said to provide adequate insect repellent properties, e.g., those set forth in U.S. Pat. No. 2,043,941 which indicates the repellency properties of methallyl disulfide and those set forth in U.S. Pat. No. 4,449,987 issued on May 22, 1984 which indicates the combination of methyl heptenones, coumarin and indole for use in perfumed candles.
Unsaturated alcohols other than 1-octen-4-ol and 1-nonen-3-ol and esters thereof are known with respect to controlling insects; and several have been found to attract insects and others have been found to repel such insects. Thus, U.S. Pat. No. 4,152,422 issued on May 1, 1979 sets forth 6-nonen-1-ol in a composition of matter used as an attractant for the male Mediterranean fruit fly. Chem. Abstracts Vol. 103, No. 71086p concerns the synthesis of (Z)-8-dodecen-1-ol and its acetate as pheromone components of the Oriental Fruit Moth (Grapholita molesta). This is an abstract of the article in Acta Chem. Scan Ser. B, 1985, B39(4), pages 267-72. U.S. Pat. No. 4,364,931 issued on Dec. 21, 1982 discloses the use of 9(Z)-tetradecen-1-ol acetate in attracting male white-line dart moths.
Chem. Abstracts Volume 80, 1974, at No. 117098f discloses the use of trans-6-nonen-1-ol acetate as an ovipositional attractant and stimulant of the melon fly. U.S. Pat. No. 2,254,665 issued on Sept. 1, 1941, on the other hand, discloses the use of aliphatic alcohols having from 10 to 14 carbon atoms to repel insects. Examples of the aliphatic alcohols of U.S. Pat. No. 2,254,665 are all saturated alcohols, to wit:
dodecyl alcohol; PA0 octyl alcohol; PA0 hexadecyl alcohol; PA0 tetradecyl alcohol; and PA0 undecyl alcohol. PA0 Item 5443--3-phenyl-2-octen-1-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5444--2,6-dimethyl-4-octen-3-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5445--3,6-dimethyl-5-octen-3-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5446--3-6-dimethyl-5-octen-3-ol acetate repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5447--2,7-dimethyl-5-octen-4-ol acetate repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5448--3,7-dimethyl-6-octen-1-ol repels the yellow fever mosquito from cloth at a level of "2" on a scale of 1-10. PA0 Item 5449--3,7-dimethyl-6-octen-1-ol carbanilate repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5450--3,7-dimethyl-6-octen-2-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5451--3,6-dimethyl-6-octen-3-ol repels the yellow fever mosquito from cloth at a level of "1" on a scale of 1-10. PA0 Item 5452--3,7-dimethyl-6-octen-3-ol repels the yellow fever mosquito from cloth at a level of "2" on a scale of 1-10. PA0 yellow fever mosquito: "1" on a scale of 1-10 PA0 tick at a level of "2" on a scale of 1-10. PA0 (a) perfuming to the environment surrounding the burning candle; PA0 (b) adequately insect repellent (both to house flies and mosquitoes) in the environment surrounding the material at various environmental temperatures at atmospheric pressure, from a temperature of about 0.degree. C. up to a temperature of about 50.degree. C.; and PA0 (c) substantially so substantive that the perfuming property as well as the insect repellent property will last for a period of time well beyond the removal of the burning candle from the environment which is being perfumed and exposed to the insect repellent. PA0 (a) from about 35% up to about 85% by weight of an oil which is normally liquid at room temperature which may be light mineral oil or a natural oil; PA0 (b) from about 7% up to 40% by weight of a long chain polyamide having a molecular weight of between 6,000 and 9,000 and a softening point within the range of 185.degree. C.-198.degree. C.; and PA0 (c) from about 7% up to about 30% by weight of an alcohol which may be a C.sub.8 -C.sub.12 primary alcohol. PA0 "The inclusion in the composition of certain alcohols that produce otherwise desirable properties may result in a material that burns with an acrid or pungent odor. In such cases a small amount of an odor masking agent can be incorporated in the composition. The material sold by Fritzche, Dodge and Olcott as its 41984 has been found to have satisfactory results. If desired, a small amount of perfume can be added to the composition to complete the odor-masking effect." PA0 Item 2891--2,6-dimethyl-4-octen-3-ol PA0 Item 2892--3,6-dimethyl-5-octen-3-ol PA0 Item 2893--3-7-dimethyl-6-octen-3-ol PA0 Item 2894--3,7-dimethyl-6-octen-2-ol PA0 Item 2895--3,7-dimethyl-6-octen-3-ol have attractancies for insects as follows: PA0 Item 2891--2,6-dimethyl-4-octen-3-ol: the Oriental Fruit Fly at a level of "1" on a scale of 1-3; the Mediterranean Fruit Fly at a level of "2" on a scale of 1-3 and the Mexican Fruit Fly at a level of "1" on a scale of 1-3. PA0 Item 2892--3,6-dimethyl-5-octen-3-ol: the Oriental Fruit Fly at a level of "1" on a scale of 1-3 and Mediterranean Fruit Fly at a level of "2" on a scale of 1-3. PA0 Item 2893--3,7-dimethyl-6-octen-1-ol: the Oriental Fruit Fly at a level of "1" on a scale of 1-3; the Mediterranean Fruit Fly at a level of "1" on a scale of 1-3; the Mexican Fruit Fly at a level of "1" on a scale of 1-3; the Gypsy Moth on a level of "1" of on a scale of 1-3; the European Chafer at a level of "1" on a scale of 1-3 and the Pink Bull Worm at a level of "1" on a scale of 1-3. PA0 Item 2894--3,7-dimethyl-6-octen-2-ol: the Meditteranean Fruit Fly at a level of "1" on a scale of 1-3; the Mexican Fruit Fly at a level of "1" on a scale of 1-3; the Gypsy Moth at a level of "1" on a scale of 1-3; the Pink Bull Worm at a level of "1" on a scale of 1-3 and the Bolweevil at level of "1" on a scale of 1-3. PA0 Item 2895--3,7-dimethyl-6-octen-3-ol: the Oriental Fruit Fly at a level of "1" on a scale of 1-3; the Mediterranean Fruit Fly at a level of "3" on a scale of 1-3; the Mexican Fruit Fly at a level of "1" on a scale of 1-3; the Pink Bull Worm at a level of "1" of 1-3 and the Bolweevil at a level of "1" on a scale of 1-3. PA0 (i) providing active and passive insect interest electronic measuring and recording means; (ii) providing enclosable insect feeding or stimulating means having controlled limited access to the external environment surrounding said apparatus and capable of being associated with said measuring and recording means, said insect feeding or stimulating means located at a fixed insect feeding or stimulating means location defined according to X, Y and Z coordinates in a first defined 3-space; said insect feeding or stimulating means consisting essentially of: PA0 (iii) providing steady state direct lighting means for supplying a beam of direct light having given substantially constant intensity and wave length or wave lengths to said feeding or stimulating means location; PA0 (iv) providing steady state air supply, air conduction and air removal means for supplying, conducting and removing air at a substantially constant mass flow rate and substantially constant linear velocity to, past and from a second 3-space immediately above said insect feeding or stimulating surface simultaneously with the supplying of said beam of direct light to said feeding or stimulating means location substantially immediately above said insect feeding or stimulating surface structure being constructed so that said measuring and recording means in sensitive to the completion of a circuit of electron flow through or proximate said conductive elements of said insect feeding or stimulating surface whereby the number and frequency of the insects attracted relative to the attractancy of said direct lighting means to the proximity of said feeding or stimulating means is capable of being determined using said measuring and recording means; PA0 (v) anaesthetizing selected insects at a location apart from said feeding or stimulating means; PA0 (vi) then supplying one or more anaesthetized insects to said first defined 3-space; PA0 (vii) then enclosing said first 3-space surrounding said feeding or stimulating means whereby access thereto is limited to said air supply, air conduction and air removal means; PA0 (viii) forming an electrical circuit connection between said feeding or stimulating means; PA0 (ix) then supplying, conducting and removing air at a substantially constant mass flow rate and substantially constant linear velocity to, past and from second defined 3-space; PA0 (x) simultaneously supplying said direct light to said second defined 3-space, the supplying of light in the air being carried out at such conditions and for such a period of time that the anaesthetized PA0 (xi) insects are de-anaesthetized and recommence life activity; and observing on said measuring and recording means the number and frequency of de-anaesthetized insects attracted to the surface or proximity of said feeding or stimulating means. PA0 (1) from 63.0 to 99.5% by weight of a soap mixture containing from 4.1 to 7% by weight of a soap of caprylic acid, from 3.8 to 7% of a soap of capric acid, from 32.1 to 45% of a soap of lauric acid, from 12 to 17.5% by weight of a soap of myristic acid, from 5.0 to 10% by weight of a soap of palmitic acid, from 1.6 to 3% by weight of a soap of stearic acid, from 3.5 to 5% by weight of a soap of oleic acid and from 0.9 to 5% by weight of a soap of linoleic acid; PA0 (2) from 0.1 to 2% by weight of one or more C.sub.8 -C.sub.18 straight chain fatty acids; PA0 (3) from 0.2 to 30% by weight of a repellent chemical; and PA0 (4) from 0.2 to 5% by weight of an effective residual insecticide.
U.S. Pat. No. 2,254,665 fails to disclose the use of unsaturated alcohols in insect repellent compositions.
Chem. Abstracts Volume 74, 1974 at No. 99419f discloses various nonenyl acetates as attractants for female melon flies (abstract of J. Med. Chem. 1971, 14(3), pages 236-9) including trans-2-nonen-1-yl acetate.
On the other hand, Beroza, Materials Evaluated as Insecticides, Repellents and Chemosterilants at Orlando and Gainesville, Fl., 1952-1964, Agriculture Handbook No. 340, published by The Agricultural Research Service, United States Department of Agriculture, August, 1967 discloses the following items 5443-5452 as insect repellents (on a scale of 1-10) as follows:
Beroza, Agriculture Handbook No. 340 at Item 7977 indicates that undecyl alcohol acetate has insect repelling properties as follows:
Formulations exist in commerce which are said to provide candle body materials that are both perfuming and insect repellent but such formulations have yielded a candle body that is either insufficiently insect repellent or aesthetically displeasing from an organoleptic standpoint.
This is so, even though it was disclosed in U.S. Pat. No. 4,759,228 that 1-nonen-3-ol can be used in such candles to repel house flies (Musca domestica L. (Diptera: Muscidae)).
The properties of the repellent compounds of our invention have advantages which render the uses thereof unexpected, unobvious and advantageous over the use, of 1-nonen-3-ol.
When a candle burns, the heat of its flame melts a small pool of the candle body material around the base of the exposed portion of the wick, and this molten material is drawn up through the wick by capillary attraction to fuel the flame. Thus, the process that takes place in the burning of a candle imposes rather stringent functional requirements upon the candle body material.
The material of a candle body must be rigid enough to support itself and a relatively long wick filament, but it should not be excessively brittle at low temperatures. Its melting point is critical in that it should liquify at temperatures to which it can be raised by radiant heat from the candle flame. If its melting temperature is too low, the candle will drip or, in an extreme case, the entire candle body will melt, dropping the wick into a pool of molten material with the hazardous possibility that the surface of the pool will ignite when this happens. If too high a temperature is required to melt the body material, the flame will be starved because insufficient fuel will be drawn up through the wick, with the result that the flame will be too small to maintain itself. When molten, moreover, the candle body material must have a relatively low viscosity in order to insure that it will be capable of being drawn up through the wick by capillary action.
In addition to meeting these requirements the candle body material must burn with a flame that is both luminous and smokeless and such odors as are produced by its combustion should not be unpleasant and should preferably be faint.
The functional requirements outlined above have, of course, been met by various candle body materials that are well known in the art, but heretofore no known materials that meet these requirements have been in combination:
The 1-nonen-3-ol of U.S. Pat. No. 4,759,228 causes the environment surrounding the burning candle to be perfumed and adequately causes house flies to be repelled but does not act in an efficacious manner with respect to the desired environmental substantivity properties as set forth supra in Section (c).
U.S. Pat. No. 3,645,705 discloses a transparent candle body composition of matter which can contain:
At column 3, line 56 of U.S. Pat. No. 3,645,705 it is disclosed that an odor masking agent may be incorporated into the candle composition. Generally this disclosure is set forth at lines 30-44 of U.S. Pat. No. 3,645,705 thusly:
Nothing in U.S. Pat. No. 3,645,705, however, discloses the applicability to the composition disclosed therein of insect repellent materials. Nothing discloses the use of a composition of matter in U.S. Pat. No. 3,645,705 which will be both a perfumant and an insect repellent.
U.S. Pat. No. 4,051,159 issued on Sept. 27, 1977 discloses a "shaped, self-supporting transparent fragrance emitting article comprising a high percentage of a thermoplastic polyamide resin having a substantially uniformly dispersed therein a C.sub.14 -C.sub.22 alkyl alcohol and a fragrance emitting material". U.S. Pat. No. 4,051,159 however, does not indicate that the compositions of matter disclosed therein are useful for fragrance candles or insect repellent.
Indeed, much of the literature teaches away from our invention as exemplied in "Materials Tested as Insect Attractants" compiled by M. Beroza and N. Green in Agriculture Handbook No. 239 in Table 2 wherein it is stated that certain methyl substituted octenals, Items Nos. 2891, 2892, 2893, 2894 and 295 to wit:
Furthermore, in Agriculture Handbook No. 239 it is stated that 3-methyl-1-nonen-3-ol has on a scale of 1-3 an attractancy of "1" for the Oriental Fruit Fly and an attractancy of "1" for the Mediterranean Fruit Fly and 4,8-dimethyl-7-nonen-4-ol has on a scale of 1 to 3 an attractancy "2" for the Oriental Fruit Fly and an attractancy of "3" for the Mediterranean Fruit Fly and an attractancy of "1" for the Mexican Fruit Fly and an attractancy of "1" for Drosophila.
With respect to any of the octenol or nonenol derivatives set forth therein the USDA Agriculture Handbook No. 239 indicates that the octenol and nonenol derivatives are neither attractants nor repellents for house flies (that is, Musca domestica).
Furthermore the U.S.D.A. Agriculture Handbook No. 239 states no information pertaining to mosquitos (e.g. Aedes aegyptae).
With respect to undecyl alcohol acetate ester, Beroza, Agriculture Handbook No. 239 discloses as Item 376 the said undecyl ester of acidic acid and indicates that the Oriental Fruit Fly is attracted at a level of "1" on a scale of 1 to 3 and the Gypsy Moth is attracted at a level of "1" on a scale of 1 to 3.
Wilson, et al., U.S. Pat. No. 4,801,446 issued on Jan. 31, 1989 describes the uses of methyl-isoeugenol having the structure: ##STR8## n-dodecanol having the structure: ##STR9## and 1-(2-butenoyl)-2,6,6-trimethyl-1,3-cyclohexadiene having the structure: ##STR10## taken alone or taken in combination as attractants for house flies (Musca domestica L. (Diptera: Muscidae)) and stored products moths. The structure of 1-(2-butenoyl)-2,6,6-trimethyl-1, 3-cyclohexadiene is different from the structures of any of the ketones useful in the instant invention which in any event are repellents rather than attractants.
As stated supra, U.S. Pat. No. 4,759,228 discloses the process and apparatus for testing insect repellency and attractancy of molecules. The apparatus of U.S. Pat. No. 4,759,228 for testing insect repellency and attractancy of various molecules comprises:
The apparatus of our invention and process for using same contain features which contain radical improvements over the apparatus and process disclosed and claimed in U.S. Pat. No. 4,759,228.
Various prior art techniques for studying feeding habits of insects have been found to be useful in formulating processes and apparatus for determining relative attractancy and repellency for insects. Thus, the paper "Laboratory Blood Feed of Culicoides mississippiensis (Diptera: Ceratopogonidae) Through A Reinforced Silicone Membrane" by Davis, Butler, Roberts, Reinert and Kline (J. Med. Entomol. Vol 20, 2: 177-182) discloses the preparation and use of a durable silicone membrane for feeding Culicoides mississippiensis in the laboratory. Further, the paper entitled "IN VITRO Feeding of Ornithodoros Ticks For Rearing And Assessment of Disease Transmission", Butler, Hess, Endris and Holscher, ACAROLOGY VI, Volume 2, published 1984 by Ellis Horwood Limited, Market Cross House, Cooper Street, Chichester, West Sussex, PO 191EB, England discloses the advantages of feeding of haematophagous arthropods through artificial membranes. A number of preferred embodiments of our invention include the teachings of the aforementioned papers. Accordingly, the aforementioned papers are incorporated herein by reference.
With reference to that aspect of our invention concerning insect repellent soap compositions, U.S. Pat. No. 4,707,496 issued on Nov. 17, 1987 relates to a topical insect repellent soap composition and to a method of protection using such composition. Generally, the insect repellent soap composition of U.S. Pat. No. 4,707,496 comprises:
The aroma of the caprylic acids disclosed in U.S. Pat. No. 4,707,496 cannot be considered to be asethetically pleasing and the efficacy in repelling (Musca domestica L. (Diptera: Muscidae)) of these caprylic acids and the efficacy of repelling mosquitoes (Aedes aegyptae) of these caprylic acids is relatively low compared with the efficacy in repelling such insects of the ketones, ketoesters and alcohol of our invention.